Patent application title: Structure for high temperature fuel cell system start up and shutdown

Abstract:

A fuel cell system includes a fuel cell stack and a PEM stack for
providing power to the system in a start up or shut down operating mode
and hydrogen to the fuel cell stack in a steady state operating mode.

Claims:

1. A fuel cell system, comprising:a fuel cell stack; anda means for
providing power to said system in at least one of start up or shut down
operating modes and hydrogen to said fuel cell stack in a steady state
operating mode.

2. The system of claim 1, wherein the means for providing power and
hydrogen comprises a proton conducting stack fluidly connected to the
fuel cell stack.

3. The system of claim 2, wherein the means further comprises a CPOx
reactor.

4. The system of claim 3, wherein the fuel inlet stream is provided to the
CPOx reactor in the at least one of the start up or shut down operating
modes, and to the fuel cell stack in the steady state operating mode, and
the fuel inlet stream is not provided to the CPOx reactor in the steady
state operating mode.

5. The system of claim 2, wherein the means comprises a PEM stack and the
system is configured to provide power from the PEM stack to at least one
auxiliary component of the system in the at least one of the start up or
shut down operating modes.

6. The system of claim 5, wherein the PEM stack is configured to separate
hydrogen from the fuel cell stack fuel exhaust stream and provide a
hydrogen stream to the fuel inlet stream in the steady state mode.

7. The system of claim 5, wherein the PEM stack is CO-tolerant.

8. The system of claim 1, wherein the fuel cell stack comprises a SOFC
stack or a MCFC stack.

9. The system of claim 8, further comprising a CPOx reactor which is
adapted to provide a purge gas to SOFC stack anode electrodes during the
at least one of start up or shut down modes to prevent the anode
electrodes from oxidizing.

10. The system of claim 1, wherein the means is a means for providing
power to said system in the shut down operating mode.

11. The system of claim 1, wherein the means is a means for providing
power to said system in the start up operating mode.

12. The system of claim 1, wherein the means is a means for providing
power to said system in both the start up and the shut down operating
modes.

13. A method of operating a fuel cell system comprising a fuel cell stack,
and a PEM stack, said method comprising:operating said fuel cell system
in at least one of a start up or shut down operating modes by:providing a
fuel inlet stream to the PEM stack;providing an air stream to the PEM
stack; andproviding power from the PEM stack to said system components;
andoperating said fuel cell system in a steady state operating mode
by:providing a fuel inlet stream to the fuel cell stack;providing a fuel
exhaust stream from the fuel cell stack to the PEM stack; andproviding a
hydrogen stream from the PEM stack to the fuel inlet stream.

14. The method of claim 13, wherein the fuel cell system further comprises
a CPOx reactor.

15. The method of claim 14, wherein the at least one of start up or shut
down operating modes comprises providing the fuel inlet stream to the
CPOx reactor and providing fuel reformate fuel inlet stream from the CPOx
reactor to the PEM stack.

16. The method of claim 13, wherein the steady state operating mode
comprises providing power to the PEM stack to operate the PEM stack in
electrolysis mode to separate hydrogen from fuel cell stack fuel exhaust
stream and to provide the separated hydrogen into the fuel inlet stream.

17. The method of claim 13, wherein power provided by the PEM stack in the
at least one of the start up or shut down operating modes is directed to
at least one auxiliary component of the system.

18. The method of claim 13, comprising providing power from the PEM stack
to said system components in the shut down operating mode.

19. The method of claim 13, comprising providing power from the PEM stack
to said system components in the start up operating mode.

20. The method of claim 13, comprising providing power from the PEM stack
to said system components in both the start up and the shut down
operating modes.

21. The method of claim 13, wherein the PEM stack is CO-tolerant.

22. The method of claim 13, wherein the fuel cell stack comprises a SOFC
stack or a MCFC stack.

23. The method of claim 22, further comprising providing a purge gas from
a CPOx reactor to the SOFC stack anode electrodes during at least one of
the start up or the shut down modes to prevent the anode electrodes from
oxidizing.

24. A fuel cell system, comprising:a fuel cell stack; anda PEM stack
adapted to provide power to said system in at least one of start up or
shut down operating modes and hydrogen to said fuel cell stack in a
steady state operating mode.

25. The system of claim 24, wherein the system lacks a purge gas storage
container.

Description:

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

[0001]The present application claims benefit of U.S. provisional
application 60/924,874, filed Jun. 4, 2007, which is incorporated herein
by reference in its entirety.

[0003]Fuel cells are electrochemical devices which can convert energy
stored in fuels to electrical energy with high efficiencies. High
temperature fuel cell systems, such as solid oxide fuel cell (SOFC)
systems and molten carbonate fuel cell (MCFC) systems, require
significant heat-up times to reach normal operating (steady state)
temperature and significant cool down for safe shutdown. In start up
times, a power source must be provided to drive components which are used
during the heat-up. For example, electric heaters or blowers for air
supplied to catalytic reactors must be powered. Normally, the power
supply for these start up components is either the grid or a distributed
generator such as an internal combustion engine fueled by diesel or
gasoline fuel. In some cases a battery supply, previously charged by a
battery charger powered by the grid may also be utilized. However, this
methodology is inefficient. Furthermore, during the significant heat up
time for system start up and cool down time for shutdown, a stored anode
purge gas is used to prevent anode oxidation when steam reformed fuel is
not available. The anode purge gas is stored within the system and
replenished periodically based on usage rates. The purge gas storage
container takes up valuable space in the system.

SUMMARY

[0004]In one embodiment a fuel cell system comprises a fuel cell stack and
a means for providing power to said system in at least one of start up or
shut down operating modes and hydrogen to said fuel cell stack in the
steady state operating mode. Preferably, the means for providing power
and hydrogen comprises a PEM stack fluidly connected to the fuel cell
stack.

[0005]In another embodiment, a method of operating a fuel cell system
comprising a fuel cell stack, and a PEM stack, comprising the steps of
(i) operating said fuel cell system in at least one of start up or shut
down operating modes by providing a fuel inlet stream to the PEM stack,
and providing power from the PEM stack to said system components, and
(ii) operating said fuel cell system in a steady state operating mode by
providing a fuel inlet stream to the fuel cell stack, providing a fuel
exhaust stream from the fuel cell stack to the PEM stack, and providing a
hydrogen stream from the PEM stack to the fuel inlet stream.

[0006]In another embodiment, a fuel cell system comprises a fuel cell
stack, and a PEM stack adapted to provide power to said system in at
least one of start up or shut down operating modes and hydrogen to said
fuel cell stack in a steady state operating mode.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007]FIG. 1 is a schematic diagram of a fuel cell system in start up
operating mode.

[0008]FIG. 2 is a schematic diagram of a fuel cell system in steady state
operating mode.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009]The present embodiments of the invention provide a fuel cell system
with improved efficiency in terms of power usage, fuel usage or both. In
another aspect, embodiments of the invention provide a fuel cell system
comprising a proton exchange membrane (PEM) stack for providing power to
system components during start up operating mode. In a further aspect,
the PEM stack provides hydrogen to the SOFC stack in the steady state
operating mode.

[0010]In one embodiment the fuel cell system comprises a fuel cell stack
and a means for providing power to said system in the start up and/or
shut down operating mode and hydrogen to said fuel cell stack in the
steady state operating mode. Preferably, the means for providing power
and hydrogen comprises a PEM stack. Optionally, said means comprises both
a PEM stack and a catalytic partial oxidizing reactor (CPOx). The system
can be configured such that the CPOx reactor provides fuel to the PEM
stack which in turn powers the system components during the start up
and/or shut down operating mode. The PEM stack can be operated to provide
hydrogen instead of power in the steady state operating mode.

[0011]In another embodiment, a method of operating a fuel cell system
comprising a SOFC stack, a CPOx reactor and a PEM stack, comprises the
steps of (a) operating said fuel cell system in a start up and/or shut
down operating mode by providing a fuel inlet stream to the CPOx reactor,
providing a fuel stream from the CPOX reactor to the PEM stack and
providing power from the PEM stack to the system components and (b)
operating the fuel cell system in a steady state operating mode by
providing a fuel stream to the SOFC stack and providing a stream of
hydrogen from the PEM stack to the fuel inlet stream.

[0012]The above described fuel cell systems are very power-efficient in
the start up mode. A very small battery set may be used to provide power
while the CPOx reactor is started and the PEM stack is heated. Following
this, the system is self-sustaining. Therefore, the required energy for
start up via either grid, distributed gen-set (diesel generator), or
battery set is significantly reduced. Furthermore, when comparing the
system with a prior art system containing the distributed diesel
generator, start up emissions and CO2 penalty is reduced because
power for start up is generated by a PEM fuel cell.

[0013]Another attractive aspect of the system is that for fuels cell
systems already employing a PEM stack for hydrogen for H2
purification, H2 generation or efficiency enhancement, the PEM stack
also doubles as a power generating unit in the start up and/or shut down
mode. In another embodiment of the invention, the system also produces an
anode oxide preventing purge gas (e.g., a gas that prevents a metal in
the anode electrode, such as nickel, from oxidizing and forming a metal
oxide, such as nickel oxide), negating the need to store special anode
oxide preventing purge gas in the system. This reduces the overall system
footprint and the servicing associated with refilling the anode purge gas
tanks. The purge gas is a dilute fuel generated on demand from the fuel
inlet stream (such as a natural gas inlet stream) by the CPOx reactor.
Such dilute fuel is acceptable for hot box emergency purging.

[0014]Generally, a fuel cell system may be regarded as operating in the
start up mode when the main power generating fuel cell stack (e.g. SOFC
stack) has not reached operating conditions (e.g. high enough
temperature.) Once the desired conditions are achieved, the system may be
placed in the steady state operation mode, by for example redirecting
and/or introducing fuel and power to various components. Once the system
is shut down, it is in shut down mode while it cools down. As such, the
fuel inlet stream is switcheably provided to certain units such as, but
not limited to, the CPOx reactor and the SOFC stack.

[0015]The present embodiments include operating the aforementioned fuel
cell systems in start up and/or shut down mode, steady state mode or
both. Furthermore, the methods described herein may be carried out while
switching from start up to steady state mode, from steady state mode to
shut down mode or both. The SOFC stack is heated (started) or cooled
(shut down) by regulating the SOFC air flow and reformate (i.e., reformed
fuel) flow rates.

[0016]In a particular embodiment, a fuel cell system is switched from the
steady state mode to the start up mode. As such, the PEM stack is
switched from hydrogen pumping mode (electrolysis mode) to power
generating mode (fuel cell mode), for example to power up heating units.
This may be desirable for various reasons such as when there is a failure
of the main balance of plant (BOP) or high temperature stack hot box in
order to keep that structure hot and protected while waiting for service
personnel to arrive. Alternatively, the fuel cell system is switched from
the steady state mode to the shut down mode. The PEM stack is switched
from hydrogen pumping mode (electrolysis mode) to power generating mode
(fuel cell mode), to provide power to auxiliary components while the
system cools down.

[0017]The examples provided herein describe fuel cell systems preferably
comprising a SOFC stack. However, it should be readily understood by one
skilled in the art that other fuel cell types, such as MCFCs, may be
equally applicable. A detailed description of a SOFC system is described
in U.S. patent applications Ser. No. 11/491,487 (filed Jul. 24, 2006),
Ser. No. 11/002,681 (filed Dec. 3, 2004) and Ser. No. 11/730,255 (filed
Mar. 30, 2007) all hereby incorporated by reference in their entirety.

[0018]A non-limiting example of a fuel cell system 100 in start up and/or
shut down mode is shown in FIG. 1. The fuel cell system 100 contains a
fuel cell stack 101, such as a solid oxide fuel cell stack (illustrated
schematically to show one solid oxide fuel cell of the stack containing a
ceramic electrolyte, such as yttria or scandia stabilized zirconia, an
anode electrode, such as a nickel-stabilized zirconia cermet, and a
cathode electrode, such as lanthanum strontium manganite). During the
start up and/or shut down operating mode, air and fuel are provided to a
CPOx reactor 155 via a CPOx air blower 157 and a hydrocarbon fuel inlet
conduit 111 respectively (see FIG. 1). The air valve 165 directs air from
blower 151 to PEM stack 1, and shuts off the air inlet conduit 167 to the
SOFC stack 101. A fuel inlet valve 163 is switched to direct the fuel
inlet stream to the CPOx reactor. As shown, fuel flow to the fuel
humidifier 119 is switched off. The reformate produced in the CPOx
reactor 155 is then provided to the PEM stack 1 through the SOFC stack
101. Alternatively, during the start up and/or shut down mode, the
reformate from the CPOx reactor 155 bypasses the SOFC stack 101. The
reformate generated in the CPOx reactor 155 is hydrogen rich and also
contains CO gas. The reformate is used as a purge gas to prevent anode
oxidation during start up and shut down. Therefore, the PEM stack 1
utilized is preferably CO tolerant. The PEM stack typically requires
lower operating temperatures than the SOFC stack. During start up mode,
electric heaters or CPOx reactor heat could be used to heat the PEM stack
to normal operating temperature.

[0019]The PEM stack 1 consumes reformate and oxygen provided by the main
cathode blower 151, to produce DC power. If desired, a single air blower
may be used in place of separate blowers 151 and 157. The DC power can be
converted to AC, and used to power auxiliary components (not shown) of
the fuel system. As used herein "auxiliary component" includes
essentially any component in a typical fuel cell system which requires
power during the start up and/or shut down mode. The air and fuel exhaust
streams of the PEM stack 1 are directed to an anode tail gas oxidizer 161
(ATO) via conduits 7 and 171 and valve 169. While the ATO is shown
separately from the stack 101, the ATO may be thermally integrated with
the reformer 123 and stack 101 as described in U.S. application Ser. No.
11/002,681 filed on Dec. 3, 2004, and incorporated herein by reference in
its entirety.

[0020]A non-limiting example of the system in steady state operation mode
is shown in FIG. 2. Once the system 100 reaches the steady state mode,
the PEM cell stack 1 is operated in H2 pumping mode (electrolysis)
to separate hydrogen from the SOFC stack 101 fuel exhaust stream.
Accordingly, power and the SOFC fuel exhaust stream are provided to the
PEM stack 1, which generates a hydrogen stream that can be combined with
the SOFC fuel inlet stream, for example at the hydrocarbon fuel inlet
conduit 111, via the hydrogen cooler 129. This feature can enhance the
system efficiency since the hydrogen stream can be combined with the fuel
inlet stream to increase the concentration of hydrogen therein. In this
mode, the fuel inlet valve 163, is switched to close fuel flow to the
CPOx reactor 155 and allow fuel flow to the humidifier 119, and
eventually the SOFC stack 101. The air valve 165 is switched to provide
air to the SOFC stack air inlet conduit 167 and closes off the air inlet
to PEM stack 1.

[0021]In order to increase the working life of the PEM stack 1, an inert
purge gas could be flowed through the stacks prior to switching operating
modes. Alternatively, instead of flowing a purge gas through the PEM
stack 1, it is possible to electrochemically prepare the PEM stack for
the transition between fuel cell mode (power generating) and H2
pumping (electrolysis) mode. If the PEM stack has been operating in
H2 pumping mode, the hydrogen from the H2 pump "cathode" may be
pumped to the anode, creating a vacuum on the "cathode." Then, air may be
flowed to the cathode without risk of H2+O2 oxidation reaction
damaging the cell. If the PEM stack has been operating in fuel cell mode,
the anode and cathode terminals may be shorted through a resistor,
thereby causing a reaction between anode hydrogen and cathode oxygen.
After this is completed, pumping may be initiated when the fuel cell
voltage has dropped to zero, indicating that oxygen reactant is depleted
from the fuel cell "cathode."

[0022]Any suitable proton conducting stack may be used in stack 1, such as
PEM stacks using Nafion membranes with CO tolerant catalysts, PBI
membranes (phosphoric acid loaded membranes) adapted for operating at
elevated temperatures, and solid acid electrolytes, all of which are
examples of proton conducting fuel cell which could operate either in
fuel cell mode or in H2 pumping mode as desired.

[0023]The PEM stack 1 shown in the embodiments FIGS. 1 and 2 may
optionally be a cascaded PEM stack. In the hydrogen pump mode this unit
electrochemically separates hydrogen from the fuel exhaust stream in the
steady state operation mode. The PEM stack 1 may comprise any suitable
proton exchange membrane device comprising a polymer electrolyte. The
hydrogen diffuses through the polymer electrolyte under an application of
a potential difference between anode and cathode electrodes located on
either side of the electrolyte. The anode, cathode, and polymer
electrolyte together comprise a membrane cell. In a cascaded PEM stack,
several sets of cells are arranged in process fluid flow series so that
the exhaust from one set of cells is used as an input for the next set of
cells. In each set of two or more cells, at least two cells are arranged
in parallel, such that the input stream is divided among the cells in the
set. In other words, any one cell in one set is in process fluid flow
series configuration with any one other cell in a different set, but all
cells in each set are preferably in process fluid flow parallel
configuration with respect to each other. The PEM stack 1 may contain two
or more sets of cells, such as three to five sets of cells. Each set of
cells may contain one or more cells, such as one to twenty cells.
Preferably, but not necessarily, each set contains more cells than the
set(s) located downstream from it. For example, in a case of a PEM stack
having three sets of cells arranged in series, the PEM stack separates
hydrogen from the exhaust stream in a three step sequence. First, a
quantity (X) of fuel exhaust is provided simultaneously to a first set of
cells having for example four cells, and a first portion (A) of hydrogen
is separated. Second, a remaining quantity (X-A) of fuel exhaust is
provided to a second set of cells having for example two cells, and a
second portion (B) of hydrogen is separated. Third, a remaining quantity
(X-A-B) of fuel exhaust is provided to the third set of cells having one
cell, and a third portion (C) of hydrogen is separated. With reference to
FIG. 2, the separated hydrogen (A+B+C) can be provided into conduit 7
through output 8. The remaining portion of the fuel exhaust consisting
essentially of carbon dioxide and water is provided into conduit 9
through output 10. The total quantity of separated hydrogen (A+B+C) is at
least 95%, such as 95% to about 100% of the hydrogen contained in the
quantity (X) of fuel exhaust provided to the PEM stack 1. The term
"hydrogen" as used herein excludes hydrocarbon hydrogen atoms. For
example, hydrogen includes molecular hydrogen (H2).

[0024]Preferably, the PEM stack 1 comprises a stack of carbon monoxide
tolerant electrochemical cells, such as a stack of high-temperature,
low-hydration ion exchange membrane cells. This type of cell includes a
non-fluorinated ion exchange ionomer membrane, such as, for example, a
polybenzimidazole (PBI) membrane, located between anode and cathode
electrodes. The membrane is doped with an acid, such as sulfuric or
phosphoric acid. An example of such cell is disclosed in US published
application US 2003/0196893, incorporated herein by reference in its
entirety. These cells generally operate in a temperature range of above
100 to about 200 degrees Celsius. Thus, the heat exchangers in the system
100 preferably keep the fuel exhaust stream at a temperature of about 120
to about 200 degrees Celsius, such as about 160 to about 190 degrees
Celsius.

[0025]Also preferably, the PEM stack utilized should have at least all
four of anode inlet, anode outlet, cathode inlet and cathode outlet flow
connections. This facilitates functioning in both H2 pumping mode
and fuel cell mode.

[0026]The system 100 also contains the first conduit 3 which operatively
connects a fuel exhaust outlet 103 of the fuel cell stack 101 to a first
inlet 2 of the PEM stack 1. The system also contains a second conduit 7
which operatively connects a first outlet 8 of the PEM stack 1 to a fuel
inlet 105 of the fuel cell stack 101. Preferably, the system 100 lacks a
compressor which in operation compresses the fuel cell stack fuel exhaust
stream to be provided into the PEM stack 1. The system 100 also contains
a third conduit 9 which operatively connects a second outlet 10 of the
PEM stack 1 to an exhaust waste containment unit 21, such as a carbon
dioxide storage tank for sequestering exhaust waste, such as carbon
dioxide and/or water. Preferably, the conduit 9 is also connected to a
dryer 20 that separates the carbon dioxide from the water contained in
the exhaust stream. The dryer 20 can use any suitable means for
separating carbon dioxide from water, such as separation based on
differences in melting point, boiling point, vapor pressure, density,
polarity, or chemical reactivity. Preferably, the separated carbon
dioxide is substantially free of water and has a relatively low dew
point. Preferably, the separated carbon dioxide is sequestered in the
containment unit 21 in order to minimize greenhouse gas pollution by the
system 100.

[0027]The system 100 further preferably contains a fuel humidifier 119
having a first inlet operatively connected to a hydrocarbon fuel source,
such as the hydrocarbon fuel inlet conduit 111, a second inlet
operatively connected to the fuel exhaust outlet 103, a first outlet
operatively connected to the fuel cell stack fuel inlet 105, and a second
outlet operatively connected to the dryer 20. In operation, the fuel
humidifier 119 humidifies a hydrocarbon fuel inlet stream from conduit
111 containing the recycled hydrogen using water vapor contained in a
fuel cell stack fuel exhaust stream. The fuel humidifier may comprise a
polymeric membrane humidifier, such as a Nafion® membrane humidifier,
an enthalpy wheel or a plurality of water adsorbent beds, as described
for example in U.S. Pat. No. 6,106,964 and in U.S. application Ser. No.
10/368,425, which published as U.S. Published Application Number
2003/0162067, all of which are incorporated herein by reference in their
entirety. For example, one suitable type of humidifier comprises a water
vapor and enthalpy transfer Nafion® based, water permeable membrane
available from Perma Pure LLC. The humidifier passively transfers water
vapor and enthalpy from the fuel exhaust stream into the fuel inlet
stream to provide a 2 to 2.5 steam to carbon ratio in the fuel inlet
stream. The fuel inlet stream dew point temperature may be raised to
about 80 to about 90 degrees Celsius in the humidifier.

[0028]The system 100 also contains a recuperative heat exchanger 121 which
exchanges heat between the stack fuel exhaust stream and the hydrocarbon
fuel inlet stream being provided from the humidifier 119. The heat
exchanger helps to raise the temperature of the fuel inlet stream and
reduces the temperature of the fuel exhaust stream so that it may be
further cooled downstream and such that it does not damage the
humidifier.

[0029]If the fuel cells are external fuel reformation type cells, then the
system 100 contains a fuel reformer 123. The reformer 123 reforms a
hydrocarbon fuel containing inlet stream into hydrogen and carbon
monoxide containing fuel stream which is then provided into the stack
101. The reformer 123 may be heated radiatively, convectively and/or
conductively by the heat generated in the fuel cell stack 101 and/or by
the heat generated in an optional burner/combustor, as described in U.S.
patent application Ser. No. 11/002,681, filed Dec. 2, 2004, which
published as U.S. Published Application Number 2005/0164051, incorporated
herein by reference in its entirety. Alternatively, the external reformer
123 may be omitted if the stack 101 contains cells of the internal
reforming type where reformation occurs primarily within the fuel cells
of the stack.

[0030]Optionally, the system 100 also contains an air preheater heat
exchanger 125. This heat exchanger 125 heats the air inlet stream being
provided to the fuel cell stack 101 using the heat of the fuel cell stack
fuel exhaust. If desired, this heat exchanger 125 may be omitted.

[0031]The system 100 also preferably contains an air heat exchanger 127.
This heat exchanger 127 further heats the air inlet stream being provided
to the fuel cell stack 101 using the heat of the fuel cell stack air
(i.e., oxidizer or cathode) exhaust. If the preheater heat exchanger 125
is omitted, then the air inlet stream is provided directly into the heat
exchanger 127 by a blower or other air intake device. The system also
optionally contains a hydrogen cooler heat exchanger 129 which cools the
separated hydrogen stream provided from unit 1, using an air stream, such
as an air inlet stream.

[0032]The system may also contain an optional water-gas shift reactor 128.
The water-gas shift reactor 128 may be any suitable device which converts
at least a portion of the water in the fuel exhaust stream into free
hydrogen. For example, the reactor 128 may comprise a tube or conduit
containing a catalyst which converts some or all of the carbon monoxide
and water vapor in the fuel exhaust stream into carbon dioxide and
hydrogen. Preferably, the reactor 128 lowers the concentration of the
remaining methane and carbon monoxide in the fuel exhaust stream to trace
levels, such as less than about 1,500 ppm. Thus, the reactor 128
increases the amount of hydrogen in the fuel exhaust stream. The catalyst
may be any suitable catalyst, such as a iron oxide or a chromium promoted
iron oxide catalyst. The reactor 128 may be located between the fuel heat
exchanger 121 and the air preheater heat exchanger 125.

[0033]During steady state mode, the fuel inlet stream is provided into the
fuel cell stack 101 through fuel inlet conduit 111. The fuel may comprise
any suitable fuel, such as a hydrocarbon fuel, including but not limited
to methane, natural gas which contains methane with hydrogen and other
gases, propane, methanol, ethanol or other biogas, or a mixture of a
carbon fuel, such as carbon monoxide, oxygenated carbon containing gas,
such as ethanol, methanol, or other carbon containing gas with a hydrogen
containing gas, such as water vapor, H2 gas or their mixtures. For
example, the mixture may comprise syngas derived from coal or natural gas
reformation.

[0034]The fuel inlet stream passes through the humidifier 119 where
moisture is added to the fuel inlet stream. The humidified fuel inlet
stream then passes through the fuel heat exchanger 121 where the
humidified fuel inlet stream is heated by the fuel cell stack fuel
exhaust stream. The heated and humidified fuel inlet stream is then
provided into a reformer 123, which is preferably an external reformer.
For example, reformer 123 may comprise a reformer described in U.S.
patent application Ser. No. 11/002,681, filed on Dec. 2, 2004, which
published as U.S. Published Application Number 2005/0164051, incorporated
herein by reference in its entirety. The fuel reformer 123 may be any
suitable device which is capable of partially or wholly reforming a
hydrocarbon fuel to form a carbon containing and free hydrogen containing
fuel. For example, the fuel reformer 123 may be any suitable device which
can reform a hydrocarbon gas into a gas mixture of free hydrogen and a
carbon containing gas. For example, the fuel reformer 123 may comprise a
nickel and rhodium catalyst coated passage where a humidified biogas,
such as natural gas, is reformed via a steam-methane reformation reaction
to form free hydrogen, carbon monoxide, carbon dioxide, water vapor and
optionally a residual amount of unreformed biogas. The free hydrogen and
carbon monoxide are then provided into the fuel (i.e., anode) inlet 105
of the fuel cell stack 101. Thus, with respect to the fuel inlet stream,
the humidifier 119 is located upstream of the heat exchanger 121 which is
located upstream of the reformer 123 which is located upstream of the
stack 101.

[0035]The air or other oxygen containing gas (i.e., oxidizer) inlet stream
is preferably provided into the stack 101 from blower 151 through valve
165 conduit 167 and through a heat exchanger 127, where it is heated by
the air (i.e., cathode) exhaust stream from the fuel cell stack. If
desired, the air inlet stream may also pass through the hydrogen cooler
heat exchanger 129 and/or through the air preheat heat exchanger 125 to
further increase the temperature of the air before providing the air into
the stack 101. Preferably, no fuel is combusted with air.

[0036]Once the fuel and air are provided into the fuel cell stack 101, the
stack 101 is operated to generate electricity and a hydrogen containing
fuel exhaust stream. About 25% of the input fuel exits the fuel exhaust
outlet 103 of the stack. The fuel exhaust stream (i.e., the stack anode
exhaust stream) is provided from the stack fuel exhaust outlet 103 into
the PEM stack 1. At least 95% of hydrogen contained in the fuel exhaust
stream is separated in the PEM stack 1, for example at least 99%, such as
about 100%, of the hydrogen contained in the fuel exhaust stream is
separated in the unit 1. The hydrogen separated from the fuel exhaust
stream in the PEM stack 1 can be then provided back into the fuel inlet
stream. Preferably, the hydrogen is provided back into the fuel inlet
conduit 111 upstream of the humidifier 119. The exhaust stream is
provided to the dryer 20 which separates carbon dioxide from water. The
separated carbon dioxide is provided through conduit 22 for sequestration
in tank 21. For example, if the fuel cell stack 101 comprises a solid
oxide regenerative fuel cell stack, then with the aid of a Sabatier
reactor, the sequestered carbon dioxide can be used to generate a
hydrocarbon fuel, such as methane, when the stack 101 operates in the
electrolysis mode, as described in U.S. Pat. No. 7,045,238, incorporated
herein by reference in its entirety. The separated water from dryer 20 is
available for humidification of the fuel inlet stream or other industrial
uses. For example, conduit 23 may provide the water from the dryer 20
back into the humidifier 119, into a steam generator (not shown) and/or
directly into the fuel inlet conduit 111.

[0037]The fuel exhaust stream is provided into the PEM stack 1 as follows.
The fuel exhaust stream may contain hydrogen, water vapor, carbon
monoxide, carbon dioxide, some unreacted hydrocarbon gas, such as methane
and other reaction by-products and impurities. This exhaust stream is
first provided into the heat exchanger 121, where its temperature is
lowered, preferably to less than 200 degrees Celsius, while the
temperature of the fuel inlet stream is raised. If the water-gas shift
reactor 128 and the air preheater heat exchanger 125 are present, then
the fuel exhaust stream is provided through the reactor 128 to convert at
least a portion of the water vapor and a majority of the residual carbon
monoxide into carbon dioxide and hydrogen. The fuel exhaust stream is
then passed through the heat exchanger 125 to further lower its
temperature while raising the temperature of the air inlet stream. The
temperature may be lowered to 120 to 180 degrees Celsius for example.

[0038]The fuel exhaust stream is then provided into inlet 2 of the PEM
stack 1 via conduit 3. During the separation step in PEM stack 1, at
least a majority of the hydrogen, such as at least 95% of the hydrogen in
the fuel exhaust stream, diffuses through the electrolyte of the cells in
the PEM stack 1, while allowing the water vapor, carbon dioxide, and any
remaining trace amounts of carbon monoxide and hydrocarbon gas in the
fuel exhaust stream to be passed through conduit 9 to the humidifier 119.
Preferably, the PEM stack 1 separates at least 99% of the hydrogen in the
fuel exhaust stream, such as about 100%.

[0039]In the fuel humidifier 119, a portion of the water vapor in the fuel
exhaust stream is transferred to the fuel inlet stream to humidify the
fuel inlet stream. The hydrocarbon and hydrogen fuel inlet stream mixture
is humidified to 80 C to 90 C dew point. The remainder of the fuel
exhaust stream is then provided into the dryer 20. The dryer 20 then
separates the carbon dioxide from the water contained in the exhaust
stream. The dry, substantially hydrogen free separated carbon dioxide is
then provided to the containment unit 21 for sequestration, and the
separated water is available for humidification of the fuel inlet stream
or other industrial uses. Thus, the environmentally friendly system
preferably contains no burner and the fuel exhaust is not combusted with
air. The only exhaust from the system consists of three streams--water,
sequestered carbon dioxide and oxygen depleted air cathode exhaust stream
through conduit 25.

[0040]The hydrogen separated from the fuel exhaust stream is then removed
from PEM stack 1 through outlet 8 and conduit 7 and provided into the
hydrocarbon fuel inlet stream in the fuel inlet conduit 111 with valve
169 closing off flow to ATO 161. If desired, prior to being provided to
the fuel inlet conduit, the hydrogen stream may be passed through a
hydrogen cooler heat exchanger 129, where the hydrogen stream exchanges
heat with an air stream, such as the air inlet stream provided into the
fuel cell stack 101. The temperature of the hydrogen stream is lowered in
the heat exchanger 129 before being provided into the fuel inlet conduit,
while the temperature of the air inlet stream is raised. Thus, the
hydrocarbon fuel inlet stream is mixed with a low dew point, near ambient
temperature recycled hydrogen recovered from the anode tail gas with a
PEM stack 1.

[0041]Thus, with respect to the fuel exhaust stream, the heat exchanger
121 is located upstream of the reactor 128, which is located upstream of
the heat exchanger 125, which is located upstream of the PEM stack, which
is located upstream of the humidifier 119 and the fuel inlet conduit 111.

[0042]If desired, all or a portion of the hydrogen separated from PEM
stack 1 may be provided to a hydrogen using device, such as a PEM fuel
cell in a vehicle or another hydrogen using device or to a hydrogen
storage vessel. In this case, a selector valve may be placed in conduit 7
to either split the hydrogen stream between the fuel inlet conduit 111
and the hydrogen storage vessel or hydrogen using device, or to alternate
the hydrogen flow between the fuel inlet conduit 111 and the hydrogen
storage vessel or hydrogen using device. Any component of the system 100
may be operated by a computer or an operator to controllably vary the gas
flow based on one or more of the following conditions: i) detected or
observed conditions of the system 100 (i.e., changes in the system
operating conditions requiring a change in the amount of hydrogen in the
fuel inlet stream); ii) previous calculations provided into the computer
or conditions known to the operator which require a temporal adjustment
of the hydrogen in the fuel inlet stream; iii) desired future changes,
presently occurring changes or recent past changes in the operating
parameters of the stack 101, such as changes in the electricity demand by
the users of electricity generated by the stack, changes in price for
electricity or hydrocarbon fuel compared to the price of hydrogen, etc.,
and/or iv) changes in the demand for hydrogen by the hydrogen user, such
as the hydrogen using device, changes in price of hydrogen or hydrocarbon
fuel compared to the price of electricity, etc.

[0043]It is believed that by recycling at least a portion of the hydrogen
from the fuel exhaust (i.e., tail) gas stream into the fuel inlet stream,
a high efficiency operation of the fuel cell system is obtained.
Furthermore, the overall fuel utilization is increased. For example, at
least 95% of the hydrogen in the fuel exhaust is separated by the PEM
stack 1 and recycled back to the stack 101. Preferably at least 99%, such
as about 100%, of the fuel exhaust gas hydrogen is separated by the PEM
stack 1 and recycled back to the stack 101. The "overall" or "effective"
fuel utilization of a system having a given "per pass" fuel utilization
rate is typically greater than the percentage of hydrogen recycled by
such a system. For example, a system that recycles only 85% of the fuel
exhaust gas hydrogen has an effective fuel utilization of about 94% to
about 95%, if its per pass utilization is about 75%. Such a system would
have an AC electrical efficiency of about 50% to about 60%, such as about
54% to 60%. In contrast, if the instant system PEM stack 1 includes a
cascaded PEM stack 1, which recycles at least 95% of exhaust hydrogen, it
then operates at a higher overall fuel efficiency (greater than 95%) and
a higher AC electrical efficiency greater than 60%. Even higher
efficiency may be obtained by increasing the per pass fuel utilization
rate above 75%, such as about 76-80%. At steady-state, there is no need
for generating steam when steam methane reformation is used to create the
feed gas to the fuel cell. The fuel exhaust stream contains enough water
vapor to humidify the fuel inlet stream to the stack at steam to carbon
ratios of 2 to 2.5. The increase in overall fuel utilization and the
removal of heat requirement to generate steam increases the overall
electrical efficiency. In contrast, a system that does not recycle any of
the exhaust hydrogen has an AC electrical efficiency of only about 45%,
assuming equivalent per pass utilization.

[0044]The fuel cell system described herein may have other embodiments and
configurations, as desired. Other components may be added if desired, as
described, for example, in U.S. application Ser. No. 10/300,021, filed on
Nov. 20, 2002 and published as U.S. Published Application Number
2003/0157386, in U.S. Provisional Application Ser. No. 60/461,190, filed
on Apr. 9, 2003, and in U.S. application Ser. No. 10/446,704, filed on
May 29, 2003 and published as U.S. Published Application Number
2004/0202914, all of which are incorporated herein by reference in their
entirety. Furthermore, it should be understood that any system element or
method step described in any embodiment and/or illustrated in any figure
herein may also be used in systems and/or methods of other suitable
embodiments described above, even if such use is not expressly described.

[0045]The foregoing description of the invention has been presented for
purposes of illustration and description. It is not intended to be
exhaustive or to limit the invention to the precise form disclosed, and
modifications and variations are possible in light of the above teachings
or may be acquired from practice of the invention. The description was
chosen in order to explain the principles of the invention and its
practical application. It is intended that the scope of the invention be
defined by the claims appended hereto, and their equivalents.